Fragrance compositions

ABSTRACT

A composition comprising:
         (a) from about 0.01% to about 99%, by weight, of a fragrance oil, wherein the fragrance oil comprises about 5% or greater, by weight of fragrance oil, of a top note perfume raw material, or mixture of top note perfume raw materials, and wherein the top note perfume raw materials have a boiling point of less than, or equal to, about 250° C. at 1 atmosphere pressure;   (b) an entrapment material which is selected from the group consisting of polymers; capsules, microcapsules and nanocapsules; liposomes; pro-perfumes selected from more than 1 type of pro-chemistry; film formers; absorbents; cyclic oligosaccharides and mixtures thereof;   (c) greater than about 50% volatile solvent.       

     The present invention provides compositions wherein the light, fresh, fruity, citrus, green or delicate floral top note fragrance character remains detectable for greater than about 2 hours, preferably greater than about 4 hours, more preferably greater than about 6 hours, after the composition has been applied to the substrate.

CROSS REFERENCE TO RELATED APPLICATIONS

This is a continuation of International Application PCT/US01/17733,filed Jun. 1, 2001.

FIELD OF THE INVENTION

The present invention relates to compositions, in particular cosmeticcompositions and more particularly fragrance compositions, whichcomprise a fragrance oil, an entrapment material and greater than 50%volatile solvent, wherein the fragrance oil comprises a high level of“top note” perfume raw materials. More particularly this inventionrelates to cosmetic compositions wherein the fragrance character of the“top note” perfume raw materials remains detectable on the substrate forat least 2 hours after application. Compositions of the presentinvention are suitable for application to a wide variety of substratesbut particularly to the skin and hair.

BACKGROUND OF THE INVENTION

It has long been a feature of many types of compositions, includingcosmetic compositions, that they comprise a fragrance oil for thepurpose of delivering a pleasant smell. This can improve the overallconsumer acceptance of the composition or mask unpleasant odours. Infact, it can be the sole purpose of some compositions to impart apleasant odour to the skin, hair or other suitable substrate.

Fragrance oils used within such compositions usually comprise manydifferent perfume raw materials. Each perfume raw material used differsfrom another by several important properties including individualcharacter, volatility and the olfactory detection level (known as theodour detection threshold). By bearing in mind these differentproperties, and others, the perfume raw material can be blended todevelop a fragrance oil with an overall specific character profile. Itis usual that the character is designed to alter and develop with timeas the different perfume raw materials evaporate from the substrate andare detected by the user. For example perfume raw materials which have ahigh volatility and low substantivity are commonly used to give aninitial burst of characters such as light, fresh, fruity, citrus, greenor delicate floral to the fragrance oil which are detected soon afterapplication. Such materials are commonly referred to in the field offragrances as “top notes”. By way of a contrast, the less volatile, andmore substantive, perfume raw materials are typically used to givecharacters such as musk, sweet, balsamic, spicy, woody or heavy floralto the fragrance oil which, although may also be detected soon afterapplication, also last for longer. These materials are commonly referredto as “middle notes” or “base notes”. Highly skilled perfumers areusually employed to carefully blend perfume raw materials so that theresultant fragrance oils have the desired overall fragrance characterprofile.

To date, the physical characteristics of the perfume raw materialsthemselves have limited the overall fragrance character profiles thatcan be created by perfumers. One such limitation is that it has onlybeen possible to develop fragrance oils which impart a “top note”character for a short period of time. This is because the top noteperfume raw materials are highly volatile and are therefore rapidlyreleased from the substrate. As such, the longer lasting element of afragrance character profile has been achieved by using middle and basenotes which in turn restricts the achievable characters to musk, sweet,balsamic, spicy, woody or heavy floral and the like. Blending of higherlevels of top note perfume raw materials to a fragrance oil does notimprove the long lasting nature of the light, fresh, fruity, citrus,green, or delicate floral “top note” fragrance character, but insteadcould result in a stronger initial burst which again quickly evaporatesand does not therefore last.

It is known that consumer preference for fragrance compositions ismostly driven by the initial “top note” character. It is thereforedesirable to have a fragrance wherein the “top note” character is longlasting and perceived throughout use (ie after application of thecomposition to the substrate). It is also desirable to be able to createnew to the world fragrance character profiles wherein one, or several,well recognised “top note” characters are maintained overtime such thata unique long lasting, “top, middle and base note” character is created.As such, it would be advantageous to be able to create a fragrance oilwhich will impart, in a new way, top note fragrance characteristics to acomposition, particularly a cosmetic composition, wherein the top notecharacter is released from the composition over a substantial period oftime, and, in particular, where the top note fragrance character remainsdetectable at least two hours after application.

In the past, many attempts have been made to delay the volatilityprofiles of fragrance oils within many types of compositions to extendthe overall fragrance effect.

For instance the fragrance oil may be formulated to include a higherproportion of perfume raw materials with a low volatility and which aretherefore more substantive on the substrate. However, as discussedabove, this restricts the fragrance character that can be achieved overtime. Another approach has been to chemically, and reversibly, modifythe perfume raw materials to a pro-perfume compound which is disclosedin patent applications WO 98/47477; WO 99/43667; WO 98/07405; WO98/47478; all of which are incorporated herein by reference. Theresultant pro-perfumes are not themselves volatile but, after thechemical modification is reversed, usually by hydrolysis uponapplication to the substrate, the perfume raw material is released andcan then evaporate in the usual way. In these examples the release rateof the perfume raw materials is controlled by the reaction rate of thepro-perfume to perfume raw material transformation.

Further disclosures have discussed improving the overall longevity of afragrance by delaying the evaporation of the fragrance oils. A widevariety of techniques have been disclosed among them encapsulation ofthe perfume raw materials for example within capsules (disclosed inJP-A-58/052211, EP-A-303,461), absorbing the materials to a surface forexample by using carbon or zeolites (disclosed in U.S. Pat. No.6,033,679), occluding the release of the perfume raw materials forexample by the formation of a film (disclosed in U.S. Pat. No.3,939,099) and complexing the perfume raw materials for example by usingcyclic oligosaccharides. The prior art on this latter method includesJP-A-6/287127 and JP-A-8/176587 which disclose use of hydroxyalkylatedcyclodextrins within cosmetic compositions to sustain the effect of thefragrance; and JP-A-8/183719 and JP-A-10/120541 which discloses acombination of cyclodextrin encapsulated fragrance and non encapsulatedfragrance within a deodorant composition for prolonging the fragranceduration to at least 2 hours, all of which are incorporated herein byreference.

Whilst the compositions and disclosures of the prior art provide usefulteachings for prolonging the overall fragrance character of a cosmeticcomposition the approaches still have limitations. The pro-perfumeapproach is limited by those chemical modifications that can suitably bemade to the perfume raw materials. In addition, the prior art isrestricted by pro chemistries used, or by the use of low levels of properfumes, thus preventing the development of a fragrance oil whichexhibits a broad range of top note characters over time. On the otherhand, entrapment materials, when used in the traditional way, interactwith a broad range of perfume materials including top, middle and basenotes prolonging the overall character of the whole fragrance. As suchthe prior art does not sufficiently teach how to preferentially delayevaporation of a large range of top note perfume materials within asingle fragrance composition. In addition since, in general, entrapmentsuch as that described suppresses the evaporation of only a relativelysmall amount of the perfume raw materials, the low level of delayedrelease is often not noticeable to the user. As such the prior art doesnot adequately teach how to provide a fragrance with long lasting andnoticeable “top note” character.

Surprisingly, it has now been found that compositions, particularlycosmetic compositions, comprising a fragrance oil and a material whichis able to delay the evaporation of the fragrance oil, and wherein thefragrance oil is blended to comprise high levels of volatile “top note”perfume raw materials preferably in conjunction with a balance ofperfume raw materials with a low odour detection threshold, can be usedto create a long lasting fragrance character profile which hasprolonged, and noticeable, “top note” characteristics. In addition, ithas been found that within such fragrance oils, long lasting “top note”character can be combined with “middle and base note” characters touniquely achieve a long lasting fragrance character profile with a broadspectrum of “top, middle and base notes” that it would not have beenpossible to develop using traditional perfumery.

While not wishing to be bound by theory, it is believed that when acomposition according to the present invention is applied to a substratean association exists between the perfume raw materials and theentrapment material such that the evaporation of the perfume rawmaterials is delayed. Over time, this association breaks down resultingin release of the perfume raw materials. Since the composition comprisesa fragrance oil which has been developed with a high level of perfumeraw materials with “top note” fragrance character, the “top note”character continues to be experienced by the user over time. Inaddition, since the fragrance oil can preferably be developed with abalance of perfume raw materials with a low odour detection threshold,the user will experience a meaningful and novel fragrance characterprofile over time. This is because the perfume raw materials continue toremain detectable even though only a relatively small level is beingreleased.

In addition, because the volatilisation rate of any given ingredienthas, until now, been mainly related to its own boiling point, it has notbeen possible to obtain recurring and intermittent blooms (or pulses) ofspecific fragrance characters throughout the complete usage period.Surprisingly it has now been found that, once a substrate has beenfragranced using a composition of the present invention, the fragrancecan be refreshed over time, either naturally or deliberately, to releaseperiodic and unexpected blooms of one or several fragrance characters.Whilst not wishing to be bound by theory, it is believed that this canbe achieved by enhancing the natural decomposition rate of the fragranceoil entrapment material association for example by application of water,either naturally by breathing on the complex or by sweating, orartificially by spraying on a mist and the like. This “activation”results in the user experiencing a noticeable bloom of fragrancecharacter. Surprisingly it has been found that it is possible to“activate” this complex, and thus generate fragrance blooms, severaltimes during the wear. It is also believed that the negative consumerperception of becoming used to a scent can be minimised or prevented asa result of periodic “activation” resulting in an unexpected perceptiblealtering in the overall character of the fragrance.

It is an object of the present invention to provide compositions,particularly cosmetic compositions, which impart a long lasting andnoticeable light, fresh, fruity, citrus, green or delicate floral “topnote” fragrance character to the substrate on which they are applied.This, and other objects of this invention, will become apparent in lightof the following disclosure.

SUMMARY OF THE INVENTION

The present invention relates to a composition comprising:

-   -   (a) from about 0.01% to about 99%, by weight, of a fragrance        oil, wherein the fragrance oil comprises about 5% or greater, by        weight of the fragrance oil, of a top note perfume raw material,        or mixture of top note perfume raw materials, wherein the top        note perfume raw materials have a boiling point of less than, or        equal to, about 250° C. at 1 atmosphere pressure;    -   (b) an entrapment material which is selected from the group        consisting of polymers; capsules, microcapsules and        nanocapsules; liposomes; pro-perfumes selected from more than 1        type of pro-chemistry; film formers; absorbents; cyclic        oligosaccharides and mixtures thereof;    -   (c) greater than about 50%, by weight, volatile solvent.

This invention further relates to methods of use for such compositionsand the use of such compositions to delay the release of the volatileperfume raw materials from the substrate.

DETAILED DESCRIPTION OF THE INVENTION

All percentages and ratios used herein are by weight of the totalcomposition and all measurements made are at 25° C., unless otherwisedesignated. Unless otherwise indicated all percentages, ratios andlevels of ingredients referred to herein are based on the actual amountof the ingredient, and do not include solvent, fillers or othermaterials which may be combined with the ingredient in commerciallyavailable products.

All publications cited herein are hereby incorporated by reference intheir entirety, unless otherwise indicated.

The term “dermatologically-acceptable,” as used herein, means that thecompositions, or components thereof, are suitable for use in contactwith human skin without undue toxicity, incompatibility, instability,allergic response, and the like.

The term “safe and effective amount” as used herein means an amount of acompound, component, or composition sufficient to significantly induce apositive benefit, but low enough to avoid serious side effects, i.e. toprovide a reasonable benefit to risk ratio, within the scope of soundmedical judgement.

Active and other ingredients useful herein may be categorised ordescribed herein by their cosmetic and/or therapeutic benefit or theirpostulated mode of action. However, it is to be understood that theactive and other ingredients useful herein can in some instances providemore than one cosmetic and/or therapeutic benefit or operate via morethan one mode of action. Therefore, classifications herein are made forthe sake of convenience and are not intended to limit an ingredient tothe particularly stated application or applications listed.

The elements of these compositions are described in more detail below.

Fragrance Oil

Compositions of the present invention comprise from about 0.01% to about99%, preferably from about 0.25% to about 50%, more preferably fromabout 0.5% to about 40%, even more preferably from about 1 % to about25%, and most preferably from about 2.5% to about 25%, by weight, of thefragrance oil.

As used herein the term “fragrance oil” relates to a perfume rawmaterial, or mixture of perfume raw materials, that are used to impartan overall pleasant odour profile to a composition. As used herein theterm “perfume raw material” relates to any chemical compound which isodiferous when in an un-entrapped state, for example in the case ofpro-perfumes, the perfume component is considered, for the purposes ofthis invention, to be a perfume raw material, and the pro-chemistryanchor is considered to be the entrapment material. In addition “perfumeraw materials” are defined by materials with a ClogP value preferablygreater than about 0.1, more preferably greater than about 0.5, evenmore preferably greater than about 1.0. As used herein the term “ClogP”means the logarithm to base 10 of the octanol/water partitioncoefficient. This can be readily calculated from a programme called“CLOGP” which is available from Daylight Chemical Information SystemsInc., Irvine Calif., USA. Octanol/water partition coefficients aredescribed in more detail in U.S. Pat. No. 5,578,563.

Within the present invention, by mixing together several differentperfume raw materials a fragrance oil can be achieved which, when usedin a composition in conjunction with an entrapment material, is able toimpart a particular long lasting character, which includes “top note”characters, to the composition in which it is used. The mixture ofperfume raw materials used will be carefully chosen and blended toachieve a fragrance oil with the desired overall fragrance characterprofile.

The fragrance oil itself can comprise any perfume raw material suitablefor use in compositions, particularly cosmetic compositions. Overall thefragrance oil will most often be liquid at ambient temperatures andconsist of a single individual perfume raw material. A wide variety ofchemicals are known for fragrance uses, including materials such asaldehydes, ketones and esters. However, naturally occurring plant andanimal oils and exudates comprising complex mixtures of various chemicalcomponents are also commonly known for use as fragrances. The individualperfume raw materials which comprise a known natural oil can be found byreference to Journals commonly used by those skilled in the art such as“Perfume and Flavourist” or “Journal of Essential Oil Research”. Inaddition some perfume raw materials are supplied by the fragrance housesas mixtures in the form of proprietary speciality accords.

In order that fragrance oils can be developed with the appropriatecharacter for the present invention the perfume raw materials have beenclassified based upon two key physical characteristics:

-   -   (i) boiling point (BP) measured at 1 atmosphere pressure. The        boiling point of many fragrance materials are given in Perfume        and Flavor Chemicals (Aroma Chemicals), Steffen Arctander        (1969). Perfume raw materials for use in the present invention        are divided into volatile raw materials (which have a boiling        point of less than, or equal to, about 250° C.) and residual raw        materials (which have a boiling point of greater than about 250°        C., preferably greater than about 275° C.). Volatile raw        materials, for the purposes of this invention, are considered to        be those that impart “top note” ie light, fresh, fruity, citrus,        green or delicate floral characters to the fragrance oil and the        like. Similarly the residual perfume raw materials are        considered to be those that impart “middle or base note” ie        musk, sweet, balsamic, spicy, woody or heavy floral characters        to the fragrance oil and the like. All perfume raw materials        will preferably have boiling points (BP) of about 500° C. or        lower.    -   (ii) odour detection threshold which is defined as the lowest        vapour concentration of that material which can be olfactorily        detected. The odour detection threshold and some odour detection        threshold values are discussed in e.g., “Standardized Human        Olfactory Thresholds”, M. Devos et al, IRL Press at Oxford        University Press, 1990, and “Compilation of Odor and Taste        Threshold Values Data”, F. A. Fazzalar, editor ASTM Data Series        DS 48A, American Society for Testing and Materials, 1978, both        of said publications being incorporated by reference. Perfume        raw materials for use in the present invention can be classified        as those with a low odour detection threshold of less than 50        parts per billion, preferably less than 10 parts per billion and        those with a high odour detection threshold which are detectable        at greater than 50 parts per billion (values as determined from        the reference above).

Since, in general, perfume raw materials refer to a single individualcompound, their physical properties (such ClogP, boiling point, odourdetection threshold) can be found by referencing the texts cited above.In the case that the perfume raw material is a natural oil, whichcomprises a mixture of several compounds, the physical properties of thecomplete oil should be taken as the weighted average of the individualcomponents. In the case that the perfume raw material is a proprietaryspeciality accord the physical properties should be obtain from theSupplier.

In order to develop fragrance oils that are suitable for use in thepresent invention it is necessary that the fragrance oil comprises about5% or greater, preferably about 5% to about 99%, preferably from about5% to about 70%, more preferably from about 10% to about 60%, even morepreferably from about 25% to about 60%, and further more preferably fromabout 25% to about 40%, by weight of fragrance oil, of volatile “topnote” perfume raw materials ie with a boiling point of less than, orequal to, about 250° C. It is preferred that the fragrance oil alsocomprises from about 0.01% to about 95%, preferably from about 5% toabout 85%, more preferably from about 10% to about 60%, by weight offragrance oil, of the residual “middle and base note” perfume rawmaterials ie those with a boiling point of greater than about 250° C.Furthermore it is preferred that the weight ratio of volatile “top note”to residual “middle and base notes” perfume raw materials within thefragrance oil is in the range from about 1:20 to about 20:1, preferablyfrom about 1:10 to about 10:1, more preferably from about 8:1 to about1:2, most preferably from about 1.2:1 to about 1:1.2.

Additionally, in order to develop fragrance oils with an appropriatecharacter profile over time, it is preferred that within the fragranceoil a balance of perfume raw materials are used which have a low odourdetection threshold. It is preferred for use herein that the “top note”perfume raw materials within the fragrance oil comprise 5% or greater,by weight of the “top note” perfume raw materials, of “top note” perfumeraw materials which have an odour detection level of less than, or equalto, 50 parts per billion, preferably less than 10 parts per billion. Inaddition it is highly preferred that the “middle or base note” perfumeraw materials within the fragrance oil comprise 10% or greater, morepreferably 20% or greater and most preferably 50% or greater, by weightof the “middle or base note” raw materials, of “middle notes” or “basenotes”, or a mixture thereof, with an odour detection threshold of lessthan, or equal to, 50 parts per billion, preferably less than 10 partsper billion. Since materials with low odour detection levels can bedetected when only very small levels are present, they are particularlyuseful for developing the long lasting character of the fragrance oilreleased over time from the entrapment material. Overall it is preferredthat the whole fragrance oil comprise from about 5% to about 95%,preferably from about 20% to about 75%, more preferably from about 25%to about 50% and even more preferably from about 25% to about 40%, byweight of the fragrance oil, high odour impact perfume raw materials.

It is a further feature of the present invention that, the fragrance oilpreferably comprising a balance of perfume raw materials with a lowodour detection threshold, such that the compositions can comprise lowerlevels of fragrance oil than would traditionally be present. This can beadvantageous for minimising skin sensitisation and also for reducingoverall costs. As such, compositions of the present invention canpreferably comprise from about 1% to about 15%, more preferably fromabout 1% to about 8%, by weight, of fragrance oil.

In general a broad range of suitable perfume raw materials can be foundin U.S. Pat. Nos. 4,145,184, 4,209,417, 4,515,705, and 4,152,272.Non-limiting examples of perfume raw materials which are useful forblending to formulate fragrance oils for the present invention are givenbelow. Any perfume raw materials, natural oils or proprietary specialityaccords known to a person skilled in the art can be used within thepresent invention.

Volatile perfume raw materials (“top notes”) useful in the presentinvention are selected from, but are not limited to, aldehydes with arelative molecular mass of less than or equal to about 200, esters witha relative molecular mass of less than or equal to about 225, terpeneswith a relative molecular mass of less than or equal to about 200,alcohols with a relative molecular mass of less than or equal to about200 ketones with a relative molecular mass of less than or equal toabout 200, nitriles, pyrazines, and mixtures thereof.

Examples of volatile “top note” perfume raw materials having a boilingpoint of less than, or equal to, 250° C., with a low odour detection areselected from, but are not limited to, anethol, methyl heptinecarbonate, ethyl aceto acetate, para cymene, nerol, decyl aldehyde, paracresol, methyl phenyl carbinyl acetate, ionone alpha, ionone beta,undecylenic aldehyde, undecyl aldehyde, 2,6-nonadienal, nonyl aldehyde,octyl aldehyde. Further examples of volatile perfume raw materialshaving a boiling point of less than, or equal to, 250° C., which aregenerally known to have a low odour detection threshold include, but arenot limited to, phenyl acetaldehyde, anisic aldehyde, benzyl acetone,ethyl-2-methyl butyrate, damascenone, damascone alpha, damascone beta,flor acetate, frutene, fructone, herbavert, iso cyclo citral, methylisobutenyl tetrahydro pyran, iso propyl quinoline, 2,6-nonadien-1-ol,2-methoxy-3-(2-methylpropyl)-pyrazine, methyl octine carbonate,tridecene-2-nitrile, allyl amyl glycolate, cyclogalbanate, cyclal C,melonal, gamma nonalactone, cis 1,3-oxathiane-2-methyl-4-propyl.

Other volatile “top note” perfume raw materials having a boiling pointof less than, or equal to, 250° C., which are useful in the presentinvention, which have a high odour detection threshold, are selectedfrom, but are not limited to, benzaldehyde, benzyl acetate, camphor,carvone, borneol, bornyl acetate, decyl alcohol, eucalyptol, linalool,hexyl acetate, iso-amyl acetate, thymol, carvacrol, limonene, menthol,iso-amyl alcohol, phenyl ethyl alcohol, alpha pinene, alpha terpineol,citronellol, alpha thujone, benzyl alcohol, beta gamma hexenol, dimethylbenzyl carbinol, phenyl ethyl dimethyl carbinol, adoxal, allylcyclohexane propionate, beta pinene, citral, citronellyl acetate,citronellal nitrile, dihydro myrcenol, geraniol, geranyl acetate,geranyl nitrile, hydroquinone dimethyl ether, hydroxycitronellal,linalyl acetate, phenyl acetaldehyde dimethyl acetal, phenyl propylalcohol, prenyl acetate, triplal, tetrahydrolinalool, verdox,cis-3-hexenyl acetate.

Examples of residual “middle and base note” perfume raw materials havinga boiling point of greater than 250° C., which have a low odourdetection threshold are selected from, but are not limited to, ethylmethyl phenyl glycidate, ethyl vanillin, heliotropin, indol, methylanthranilate, vanillin, amyl salicylate, coumarin. Further examples ofresidual perfume raw materials having a boiling point of greater than250° C. which are generally known to have a low odour detectionthreshold include, but are not limited to, ambrox, bacdanol, benzylsalicylate, butyl anthranilate, cetalox, ebanol, cis-3-hexenylsalicylate, lilial, gamma undecalactone, gamma dodecalactone, gammadecalactone, calone, cymal, dihydro iso jasmonate, iso eugenol, lyral,methyl beta naphthyl ketone, beta naphthol methyl ether, para hydroxylphenyl butanone, 8-cyclohexadecen-1-one,oxocyclohexadecen-2-one/habanolide, florhydral, intreleven aldehyde.

Other residual “middle and base note” perfume raw materials having aboiling point of greater than 250° C. which are useful in the presentinvention, but which have a high odour detection threshold, are selectedfrom, but are not limited to, eugenol, amyl cinnamic aldehyde, hexylcinnamic aldehyde, hexyl salicylate, methyl dihydro jasmonate,sandalore, veloutone, undecavertol, exaltolide/cyclopentadecanolide,zingerone, methyl cedrylone, sandela, dimethyl benzyl carbinyl butyrate,dimethyl benzyl carbinyl isobutyrate, triethyl citrate, cashmeran,phenoxy ethyl isobutyrate, iso eugenol acetate, helional, iso E super,ionone gamma methyl, pentalide, galaxolide, phenoxy ethyl propionate.

Entrapment Material

Compositions of the present invention comprise an entrapment materialpreferably at a level of from about 0.1% to about 95%, preferably fromabout 0.5% to about 50%, more preferably from about 1% to about 25% andeven more preferably from about 2% to about 8%, by weight, of anentrapment material.

As defined herein an “entrapment material” is any material which, afterapplication of the composition to a substrate, suppresses the volatilityof the perfume raw materials within the fragrance oil thus delayingtheir evaporation. It is not necessary that the entrapment materialforms an association with the perfume raw material within thecomposition itself, only that this association exists on the substrateafter application of the composition. Non limiting examples ofmechanisms by which the delay in evaporation may occur are by theentrapment material reversibly or irreversibly, physically or chemicallyassociating with the perfume raw material through complexing,encapsulating, occluding, absorbing, binding, or otherwise adsorbing theperfume raw materials of the fragrance oil.

As defined herein “reversible entrapment” means that any entrapmentmaterial: perfume raw material association in which the association canbe broken down so that the entrapment material and perfume raw materialsare released from each other. As defined herein “irreversibleentrapment” means that the entrapment material: perfume raw materialassociation cannot be broken down. As defined herein “chemicallyassociated” means that the entrapment material and perfume raw materialare linked through a covalent, ionic, hydrogen or other type of chemicalbond. As defined herein “physically associated” means that theentrapment material and perfume raw material are linked through a bondwith a weaker force such as a Van der Waals force. Highly preferred isthat, upon the substrate, the entrapment material and the perfume rawmaterial form a reversible physical or chemical association.

As defined herein “to delay the evaporation of a perfume raw material”means to slow down or inhibit the evaporation rate of said perfume rawmaterial from the substrate such that the fragrance “top note” characterof the perfume raw material is detectable for at least 2 hours afterapplication to the substrate.

Entrapment materials for use herein are selected from polymers;capsules, microcapsules and nanocapsules; liposomes; pro-perfumesselected from more than 1 type of pro-chemistry; film formers;absorbents; cyclic oligosaccharides and mixtures thereof. Preferred arepro-perfumes selected from more than 1 type of pro-chemistry, absorbentsand cyclic oligosaccharides and mixtures thereof. Highly preferred arecyclic oligosaccharides.

Within the entrapment association it is preferred that the weight ratioof top note perfume raw material to entrapment material within theassociated form is in the range from about 1:20 to about 20:1, morepreferably in the range from about 1:10 to about 10:1, even morepreferably in the range from about 1:10 to about 1:4.

Complexation using for Example Cyclic Oligosaccharides

It is highly preferred for compositions of the present invention thatthe entrapment material reversibly, chemically and physically complexesthe perfume raw materials. Non limiting, and preferred, examples ofentrapment materials that can act in this way are cyclicoligosaccharides, or mixtures of different cyclic oligosaccharides.

As used herein, the term “cyclic oligosaccharide” means a cyclicstructure comprising six or more saccharide units. Preferred for useherein are cyclic oligosaccharides having six, seven or eight saccharideunits and mixtures thereof, more preferably six or seven saccharideunits and even more preferably seven saccharide units. It is common inthe art to abbreviate six, seven and eight membered cyclicoligosaccharides to α, β and γ respectively.

The cyclic oligosaccharide of the compositions used for the presentinvention may comprise any suitable saccharide or mixtures ofsaccharides. Examples of suitable saccharides include, but are notlimited to, glucose, fructose, mannose, galactose, maltose and mixturesthereof. However, preferred for use herein are cyclic oligosaccharidesof glucose. The preferred cyclic oligosaccharides for use herein areα-cyclodextrins or β-cyclodextrins, or mixtures thereof, and the mostpreferred cyclic oligosaccharides for use herein are β-cyclodextrins.

The cyclic oligosaccharide, or mixture of cyclic oligosaccharides, foruse herein may be substituted by any suitable substituent or mixture ofsubstituents. Herein the use of the term “mixture of substituents” meansthat two or more different suitable substituents can be substituted ontoone cyclic oligosaccharide. The derivatives of cyclodextrins consistmainly of molecules wherein some of the OH groups have been substituted.Suitable substituents include, but are not limited to, alkyl groups;hydroxyalkyl groups; dihydroxyalkyl groups; (hydroxyalkyl)alkylenylbridging groups such as cyclodextrin glycerol ethers; aryl groups;maltosyl groups; allyl groups; benzyl groups; alkanoyl groups; cationiccyclodextrins such as those containing 2-hydroxy-3-(dimethylamino)propyl ether; quaternary ammonium groups; anionic cyclodextrins such ascarboxyalkyl groups, sulphobutylether groups, sulphate groups, andsuccinylates; amphoteric cyclodextrins; and mixtures thereof. Othercyclodextrin derivatives are disclosed in copending application U.S.Pat. No. 09/32192 (27 ^(th) May 1999), all of which are incorporatedherein by reference.

The substituents may be saturated or unsaturated, straight or branchedchain. Preferred substituents include saturated and straight chain alkylgroups, hydroxyalkyl groups and mixtures thereof. Preferred alkyl andhydroxyalkyl substituents are selected from C₁–C₈ alkyl or hydroxyalkylgroups or mixtures thereof, more preferred alkyl and hydroxyalkylsubstituents are selected from C₁–C₆ alkyl or hydroxyalkyl groups ormixtures thereof, even more preferred alkyl and hydroxyalkylsubstituents are selected from C₁–C₄ alkyl or hydroxyalkyl groups andmixtures thereof. Especially preferred alkyl and hydroxyalkylsubstituents are propyl, ethyl and methyl, more especially hydroxypropyland methyl and even more preferably methyl.

Preferred cyclic oligosaccharides for use in the present invention areunsubstituted, or are substituted by only saturated straight chainalkyl, or hydroxyalkyl substituents. Therefore, preferred examples ofcyclic oligosaccharides for use herein are α-cyclodextrin,β-cyclodextrin, methyl-α-cyclodextrin, methyl-βcyclodextrin,hydroxypropyl-α-cyclodextrin and hydroxypropyl-β-cyclodextrin. Mostpreferred examples of cyclic oligosaccharides for use herein aremethyl-α-cyclodextrin and methyl-β-cyclodextrin. These are availablefrom Wacker-Chemie GmbH Hanns-Seidel-Platz 4, Munchen, DE under thetradename Alpha W6 M and Beta W7 M respectively. Especially preferred ismethyl-β-cyclodextrin.

Methods of modifying cyclic oligosaccharides are well known in the art.For example, see “Methods of Selective Modifications of Cyclodextrins”Chemical Reviews (1998) Vol. 98, No. 5, pp 1977–1996, Khan et al andU.S. Pat. No. 5,710,268.

In addition to preferred substituents themselves, it is also preferredthat the cyclic oligosaccharides of the compositions used for thepresent invention have an average degree of substitution of at least1.6, wherein the term “degree of substitution” means the average numberof substituents per saccharide unit. Preferred cyclic oligosaccharidesfor use herein have an average degree of substitution of less than about2.8. More preferably the cyclic oligosaccharides for use herein have anaverage degree of substitution of from about 1.7 to about 2.0. Theaverage number of substituents can be determined using common NuclearMagnetic Resonance techniques known in the art.

The cyclic oligosaccharides of the compositions used for the presentinvention are preferably soluble in both water and ethanol. As usedherein “soluble” means at least about 0.1 g of solute dissolves in 100ml of solvent, at 25° C. and 1 atm of pressure. Preferably the cyclicoligosaccharides for use herein have a solubility of at least about 1g/100 ml, at 25° C. and 1 atm of pressure. Preferred is that cyclicoligosaccharides are only present at levels up to their solubilitylimits in a given composition at room temperature. A person skilled inthe art will recognise that the levels of cyclic oligosaccharides usedin the present invention will also be dependent on the components of thecomposition and their levels, for example the solvents used or the exactfragrance oils, or combination of fragrance oils, present in thecomposition. Therefore, although the limits stated for the entrapmentmaterial are preferred, they are not exhaustive.

Encapsulation using Capsules, Micro-capsules and Nanocapsules

Encapsulation of fragrances within capsules, micro-capsules ornanaocapsules which are broken down by environmental triggers can beused to reduce the volatility of fragrance oils by surrounding the oilby small droplets as a resistant wall. This may be either watersensitive or insensitive. In the first case the fragrance is releasedwhen the encapsulated particle is affected by moisture loss from theskin; while in the second case the capsule wall must be rupturedmechanically before the fragrance is released. Encapsulation techniquesare well known in the art including DE 1,268,316; U.S. Pat. Nos.3,539,465; 3,455,838.

Moisture sensitive capsules, micro-capsules and nanocapsules arepreferably formed from, but not limited to, a polysaccharide polymer.Examples of suitable polymers are dextrins, especially low-viscositydextrins including maltodextrins. A particularly preferred example of alow viscosity dextrin is one which, as a 50% dispersion in water has aviscosity at 25° C., using a Brookfield Viscometer fitted with an “A”type T-Bar rotating at 20 rpm in helical mode, of 330±20 mPa.s. Thisdextrin is known as Encapsul 855 and is available from National Starchand Chemicals Ltd. A further example of a polysaccharide that can beused to form the moisture sensitive capsules is gum acacia.

Time release micro-capsules are also suitable for use in compositions ofthe present invention for entrapping hydrophobic perfume raw materials.Such compositions comprise the perfume raw materials encapsulated in awax or polymer matrix which in turn is coated with a compatiblesurfactant. The wax or polymers used to form the matrix have a meltingpoint in the range from about 35° C. to about 120° C. at 1 atmospherepressure. These are described in detail in EP-A-908,174.

Occlusion using Film Formers

Film formers can also be used to reduce the volatility profile ofperfume raw materials. When the fragrance is applied to a substrate,such as the skin, it is believed that film formers entrap the perfumeoils during the evaporation of the volatile solvent thus hindering therelease of the volatile material. Any film former which is compatiblewith the perfume raw materials may be used, preferably the film formerwill be soluble in water—ethanol mixture. Film former materials usefulin this invention include, but are not limited to, ionic and non-ionicderivatives of water soluble polymers. Examples of suitable film formingmaterials are water soluble polymers containing a cationic moiety suchas polyvinyl pyrrolidine and its derivatives having a molecular weightof 50,000 to 1,000,000. Other examples of ionic polymeric film formingmaterials are cationic cellulose derivatives sold under the trade namesof Polymer JR (union Carbide), Klucel GM (hercules) and ethoxylatedpolyethyleneimine sold under the trade name PEI 600 (Dow). Examples ofsuitable cellulosic derivatives such as hydroxymethyl cellulose,hydroxypropyl methylcellulose and hydroxyethyl cellulose. Anotherexamples of film formers is benzophenone.

Non limiting examples of film forming materials are given in U.S. Pat.No. 3,939,099.

Other Polymers

Additional non limiting examples of other polymer systems that can beused include water soluble anionic polymers e.g., polyacrylic acids andtheir water-soluble salts are useful in the present invention to delaythe evaporation rate of certain amine-type odours. Preferred polyacrylicacids and their alkali metal salts have an average molecular weight ofless than about 20,000, preferably less than 10,000, more preferablyfrom about 500 to about 5,000. Polymers containing sulphonic acidgroups, phosphoric acid groups, phosphonic acid groups and their watersoluble salts, and their mixtures thereof, and mixtures with carboxylicacid and carboxylate groups, are also suitable.

Water soluble polymers containing both cationic and anionicfunctionalities are also suitable. Examples of these polymers are givenin U.S. Pat. No. 4,909,986. Another example of water-soluble polymerscontaining both cationic and anionic functionalities is a copolymer ofdimethyidiallyl ammonium chloride and acrylic acid, commerciallyavailable under the trade name Merquat 280® from Calgon.

Pro-Perfumes

Synthesising pro-perfumes or pro-fragrances from perfume raw materialscan result in compounds which impart a delayed release mechanism to thatspecific perfume raw material. Pro-perfumes useful within the presentinvention include those selected from more than 1 type of pro-chemistrywhich ensures that a wide range of possible perfume raw materials can beused. This is consistent with the objective of providing uniquefragrances with a broad spectrum of “top note” characters.

Within a pro-perfume the perfume raw material has been reacted with morethan one type of chemical groups such as acetal, ketal, ester,hydrolysable inorganic-organic. As such, as defined within the presentinvention, the perfume raw material is considered to constitute part ofthe fragrance oil and the chemical groups to constitute part of theentrapment material. Pro-perfumes themselves are designed to benon-volatile, or else have a very low volatility. However, once on thesubstrate, the perfume raw material is released from the pro-perfume.Once released the perfume raw material has its original characteristics.The perfume raw material may be released from the pro-perfume in anumber of ways. For example, it may be released as a result of simplehydrolysis, or by shift in an equilibrium reaction or by a pH-change, orby enzymatic release. The fragrances herein can be relatively simple intheir compositions, comprising a single chemical, or can comprise highlysophisticated complex mixtures of natural and synthetic chemicalcomponents, all chosen to provide any desired odour.

Non-limiting pro-perfumes suitable for use in the present applicationare described in WO 98/47477, WO 99/43667, WO 98/07405, WO 98/47478 andcopending applications U.S. Ser. No. 60/105,380 (23 Oct. 1998) and U.S.Ser. No. 60/130,108 (20 Apr. 1999).

Absorption of Perfume Raw Material

When clarity of solution is not needed, odour absorbing materials suchas zeolites and/or activated carbon can be used to modify the releaserate of perfume raw materials.

A preferred class of zeolites is characterised as “intermediate”silicate/aluminate zeolites. The intermediate zeolites are characterisedby SiO₂/AlO₂ molar ratios of less than about 10, preferably in the rangefrom about 2 to about 10. The intermediate zeolites have an advantageover the “high” zeolites since they have an affinity for amine-typeodours, they are more weight efficient for odour absorption since theyhave a larger surface area and they are more moisture tolerant andretain more of their odour absorbing capacity in water than the highzeolites. A wide variety of intermediate zeolites suitable for useherein are commercially available as Valfor® CP301-68, Valfor® 300-63,Valfor® CP300-35 and Valfor® 300-56 available from PQ Corporation, andthe CBV100® series of zeolites from Conteka. Zeolite materials marketedunder the trade name Abscents® and Smellrite® available from The UnionCarbide Corporation and UOP are also preferred. These materials aretypically available as a white powder in the 3–5 μm particle size range.Such materials are preferred over the intermediate zeolites for controlof sulphur containing odours e.g., thiols, mercaptans.

Carbon materials suitable for use in the present invention are materialswell known in commercial practice as absorbents for organic moleculesand/or for air purification purposes. Often, such carbon material isreferred to as “activated” carbon or “activated charcoal”. Such carbonis available from commercial sources under trade names as; Calgon-TypeCPG®; Type PCB®; Type SGL®; Type CAL®; and Type OL®.

Other odour absorbers suitable for use herein include silica molecularsieves, activated alumina, bentonite and kaolonite.

Volatile Solvent

Compositions of the present invention comprise greater than about 50%,preferably from about 55% to about 99.9%, more preferably from about 60%to about 95%, even more preferably from about 65% to about 75%, byweight, of a volatile solvent, or mixture of volatile solvents. Anyvolatile solvent suitable for use in the compositions can be usedherein. The solvents for use herein are preferably organic volatilesolvents.

As used herein, “volatile” refers to substances with a significantamount of vapour pressure under ambient conditions, as is understood bythose in the art. The volatile solvents for use herein will preferablyhave a vapour pressure of about 2 kPa or more, more preferably about 6kPa or more at 25° C. The volatile solvents for use herein willpreferably have a boiling point under 1 atm, of less than about 150° C.,more preferably less than about 100° C., even more preferably less thanabout 90° C., even more preferably still less than about 80° C.

Preferably the volatile solvents for use herein will be safe for use ona wide range of substrates, more preferably on human or animal skin orhair. Suitable volatile solvents include, but are not limited to, thosefound in the CTFA International Cosmetic Ingredient Dictionary andHandbook, 7^(th) edition, volume 2 P1670–1672, edited by Wenninger andMcEwen (The Cosmetic, Toiletry, and Fragrance Association, Inc.,Washington, D.C., 1997). Conventionally used volatile solvents includeC₃–C₄ saturated and unsaturated, straight or branched chain hydrocarbonssuch as cyclohexane, hexane, heptane, isooctane, isopentane, pentane,toluene, xylene; halogenated alkanes such as perfluorodecalin; etherssuch as dimethyl ether, diethyl ether; straight or branched chainalcohols and diols such as methanol, ethanol, propanol, isopropanol,n-butyl alcohol, t-butyl alcohol, benzyl alcohol, butoxypropanol,butylene glycol, isopentyldiol; aldehydes and ketones such as acetone;volatile silicones such as cyclomethicones for example octamethyl cyclotetrasiloxane and decamethyl cyclopentane siloxane; volatile siloxanessuch as phenyl pentamethyl disiloxane, phenylethylpentamethyldisiloxane, hexamethyl disiloxane, methoxy propylheptamethylcyclotetrasiloxane, chloropropyl pentamethyl disiloxane, hydroxypropylpentamethyl disiloxane, octamethyl cyclotetrasiloxane, decamethylcyclopentasiloxane; propellants, and mixtures thereof. Preferredvolatile solvents are ethers such as dimethyl ether, diethyl ether;straight or branched chain alcohols and diols such as methanol, ethanol,propanol, isopropanol, n-butyl alcohol, t-butyl alcohol, benzyl alcohol,butoxypropanol, butylene glycol, isopentyldiol; volatile silicones suchas cyclomethicones for example octamethyl cyclo tetrasiloxane anddecamethyl cyclopentane siloxane; propellants, and mixtures thereof.More preferred for use herein are C_(1–C) ₄ straight chain or branchedchain alcohols for example methanol, ethanol, propanol, isopropanol andbutanol and mixtures thereof, and most preferred for use herein isethanol.

Balance of the Composition

The compositions herein are useful for use a fragrance component to awide variety of different types of compositions including those such ascosmetic compositions, fragrance compositions for human or animal use,air freshener compositions, aromatherapy compositions, laundry andcleaning compositions, fragranced paper, cloth or other substrate typeproducts and the like, in fact in any type of composition whichcomprises a fragrance. In all of these cases the compositions wouldcomprise a variety of other optional ingredients which would render thecompositions more acceptable or provide them with additional usagebenefits. Such conventional optional ingredients are well-known to thoseskilled in the art and will vary greatly depending upon the field inwhich the compositions are to be used. Although compositions accordingto the second aspect of this invention comprise greater than 50%volatile solvent they should still be considered as being useful forinclusion in a wide variety of compositions with both cosmetic and noncosmetic benefits.

For cosmetic compositions in particular, the compositions can compriseany cosmetically acceptable ingredients such as those found in the CTFAInternational Cosmetic Ingredient Dictionary and Handbook, 7^(th)edition, edited by Wenninger and McEwen, (The Cosmetic, Toiletry, andFragrance Association, Inc., Washington, D.C., 1997). As used herein“cosmetically acceptable” means a material (e.g., compound orcomposition) which is suitable for use in contact with skin, hair orother suitable substrate as defined herein below. However that theseingredients are listed as useful for inclusion within a cosmeticcomposition does not preclude them from being incorporated into anyother type of composition which comprises a fragrance formulatedaccording to the present invention.

Nonvolatile Solvents

While the compositions of the present invention must comprise a volatilesolvent they may also comprise “nonvolatile” solvents. Suitablenon-volatile solvents include, but are not limited to, benzyl benzoate,diethyl phthalate, isopropyl myristate, and mixtures thereof.

Molecular Wedges

When cyclic oligosaccharides are present in the compositions of thepresent invention, low molecular weight polyol molecular wedge havingfrom about 2 to about 12 carbon atoms, preferably from about 2 to about6 carbon atoms and at least one —OH functional group, preferably atleast 2 —OH functional groups are preferably used herein for furtherprolonging the fragrance character of the composition. These polyols canfurther contain ether groups within the carbon chain. Suitable examplesinclude ethylene glycol, propylene glycol, dipropylene glycol,1,4-butanediol, 1,6-hexanediol and mixtures thereof. When present thesepolyols are present at a level of from about 0.01% to about 20%,preferably from about 0.1% to about 10%, and especially from about 0.5%to about 5% by weight of composition. It is preferred that the molarratio of molecular wedge material to oligosaccharide is from 10:1 to1:10, preferably 1:1 or greater, especially 1:1.

While not wishing to be limited by theory, the above mentioned molecularwedge molecules can form tertiary inclusion complexes with the complexedperfume material and the cyclic oligosaccharide. These small dipolarmolcules can fit into the cavity of the cyclic oligosaccharide andanchor via their OH groups onto the outside rim of the cyclicoligosaccharide through hydrogen bonding. This enables the inclusion ofall or parts of the fragrance material into the cavity of the cyclicoligosaccharide such that the stability of the formed tertiary complexis increased versus the complex formed by the fragrance material andcyclic oligosaccharide alone.

Water

The compositions of the present invention may also comprise water. Ifpresent, the water will preferably comprise from about 0.1% to about40%, more preferably from about 1% to about 30%, even more preferablyabout 5% to about 20%, by weight, of total composition.

There are a number of other examples of additional ingredients that aresuitable for inclusion into the present compositions. These include, butare not limited to, alcohol denaturants such as denatonium benzoate; UVstabilisers such as benzophenone-2; antioxidants such as tocopherylacetate; preservatives such as phenoxyethanol, benzyl alcohol, methylparaben, propyl paraben; dyes; pH adjusting agents such as lactic acid,citric acid, sodium citrate, succinic acid, phosphoric acid, sodiumhydroxide, sodium carbonate; deodorants and anti-microbials such asfarnesol and zinc phenolsulphonate; humectants such as glycerine; oils;skin conditioning agents such as allantoin; cooling agents such astrimethyl isopropyl butanamide and menthol; hair conditioningingredients such as panthenol, panthetine, pantotheine, panthenyl ethylether, and combinations thereof; silicones; solvents such as hexyleneglycol; hair-hold polymers such as those described in WO-A-94/08557;salts in general, such as potassium acetate and sodium chloride andmixtures thereof. If present, these additional ingredients willpreferably be present at a level of less than 10%, by weight, of totalcomposition. More preferably these additional ingredients will bepresent at a level of less than 5%, by weight, of total composition.

Product Forms

The compositions for use in the present invention may take any formsuitable for use, more preferably for cosmetic use. These include, butare not limited to, vapour sprays, aerosols, emulsions, lotions,liquids, creams, gels, sticks, ointments, pastes, mousses and cosmetics(e.g., semi-solid or liquid make-up, including foundations). Preferablythe compositions for use in the present invention take the form of avapour spray. Compositions of the present invention can be further addedas an ingredient to other cosmetic compositions in which they arecompatible. As such they can be used within solid composition or appliedsubstrates etc.

The compositions for use in the present invention will preferablycomprise an acceptable carrier. The phrase “acceptable carrier”, as usedherein, means one or more compatible solid or liquid fillers, diluents,extenders and the like. The term “compatible”, as used herein, meansthat the components of the compositions of this invention are capable ofbeing combined with the primary actives of the present invention, andwith each other, in a manner such that there is no interaction whichwould substantially reduce the efficacy of the composition underordinary use situations. The type of carrier utilised in the presentinvention depends of the type of product desired and may comprise, butare not limited to, solutions, aerosols, emulsions (includingoil-in-water or water-in-oil), gels, solids and liposomes.

Preparation of Composition

Compositions and fragrance oils for use in the present invention shouldbe prepared according to procedures usually used in and that are wellknown and understood by those skilled in the art with materials ofsimilar phase partitioning can be added in any order. The entrapment ofthe perfume raw materials can occur at any reasonable stage in thepreparation of the overall composition. As such the fragrance oil can beprepared in its entirety, then entrapped with a suitable material beforeaddition to the remainder of the composition. Alternatively theentrapment material can be added to the balance of the composition priorto addition of the complete fragrance oil. Finally it is possible toentrap any single perfume raw material, or group of raw materials,individually before either adding these to the balance of the fragranceoil or to the balance of the composition.

Methods of Use

The present invention relates to compositions, preferably cosmeticcompositions, particularly fragrance compositions, which comprise afragrance oil, in combination with an entrapment material, such that thefragrance profile of highly volatile perfume raw materials preferablyremains detectable for at least 2 hours after applying the compositionto the substrate.

Therefore according to another aspect of the present invention there isprovided a composition comprising:

-   -   (a) from about 0.01% to about 99%, by weight, of a fragrance        oil, wherein the fragrance oil comprises a top note perfume raw        material, or mixture of top note perfume raw materials, wherein        the top note perfume raw materials have a boiling point of less        than, or equal to, about 250° C. at 1 atmosphere pressure;    -   (b) an entrapment material which is selected from the group        consisting of polymers; capsules, microcapsules and        nanocapsules; liposomes; pro-perfumes selected from more than 1        type of pro-chemistry; film formers; absorbents; cyclic        oligosaccharides and mixtures thereof;    -   (c) greater than about 50% volatile solvent        wherein the “top note” perfume raw material characters, or        mixture of raw material characters, remain detectable for        greater than about 2 hours, preferably greater than about 4        hours, more preferably greater than about 6 hours, after the        composition has been applied to the substrate.

The composition itself is preferably used for providing fragrance to asuitable substrate. As used herein the term “suitable substrate” meansany surface to which the present composition may be applied without anunduly adverse effect. This can include a wide range of substratesincluding human or animal skin or hair, paper, furnishings, materials,and can also include the air in a room. Preferred substrates are theskin or hair, especially the skin.

The preferred compositions of the present invention may be used in aconventional manner for fragrancing a suitable substrate. An effectiveamount of the composition, typically from about 1 μl to about 1000 μl,preferably from about 10 μl to about 250 μl, more preferably from about25 μl to about 100 μl, is applied to the substrate. The composition maybe applied by hand but is preferably applied utilising a vaporiser.Preferably, the composition is then left to dry.

Periodic blooming of the compositions of the present invention can beachieved by application, either naturally or artificially, of amaterial, such as water, which will drive the disassociation of thefragrance oil from the entrapment material. Such a bloom can be achievednaturally by seating, breathing on the fragranced substrate, rubbing thesubstrate and the like. In order to achieve such a bloom artificially itis necessary to use a refresher spray in conjunction with thecompositions described herein. Such a refresher spray should comprise amaterial such as water which is capable of driving the break down of thefragrance oil entrapment material association. The refresher spray wouldbe applied to the substrate, for example from an atomiser, whenever theboom was desired for example each hour after application of thefragrance to the substrate initially. Each time the refresher spray isapplied it is expected that fragrance blooms would be achieved. It isexpected that each fragrance bloom would last for less than about 30minutes, preferably less than about 15 minutes, more preferably lessthan about 10 minutes and even more preferably less than about 5minutes. Throughout wear a fragrance could be expected to be capable ofblooming at least about 2 times or more, preferably about 4 times ormore and more preferably about 6 times or more.

EXAMPLES

The following examples further illustrate the preferred embodimentswithin the scope of the present invention. These examples are givensolely for the purposes of illustration and are not to be construed aslimitations of the present invention as many variations of the inventionare possible without departing from its spirit or scope. Unlessotherwise indicated, all ingredients are expressed on a weightpercentage of the active ingredient.

Fragrance Oil Examples I–VII

Examples I–VII are non limiting examples of the fragrance oil.

Perfume Raw Material I (%) II (%) III (%) IV (%) V (%) VI (%) VII (%)damascone beta 0.1 0.0 0.0 1.5 0.0 0.0 0.0 allyl amyl 0.1 0.0 0.0 0.00.0 0.3 0.3 glycolate ionone beta 3 2.5 0.0 0.0 0.0 0.0 0.0 damasconealpha 0.0 0.1 0.1 3 0.2 0.1 0.2 methyl phenyl 0.0 1.7 0.0 0.0 0.0 0.40.0 carbinyl acetate cyclogalbanate¹ 0.0 0.0 1.5 0.0 0.0 0.0 0.5 methylisobutenyl 0.0 0.0 0.3 0.0 0.0 0.0 0.1 tetrahydro pyran ethyl-2-methyl0.0 0.0 0.1 0.0 0.0 0.0 0.1 butyrate fructone 0.5 0.0 2.0 0.0 0.1 0.0 1flor acetate 1 0.0 7.0 0.0 0.0 0.0 2 ionone alpha 0.5 0.0 3 3 0.3 0.0 1melonal 0.0 0.0 0.0 1.5 0.2 0.0 0.0 undecylenic 0.0 0.0 0.0 0.0 0.0 0.40.0 aldehyde Lemon Oil, Cold to 100 5 0.0 0.0 0.0 0.5 0.0 PressedBergamot Oil, 25 0.0 0.0 14.5 0.0 1.5 0.0 Eco Essence Cassis Base 345- 10.0 0.0 30 3 1.0 0.0 L² menthol 0.5 0.0 0.0 0.0 0.0 0.0 0.0 beta gamma0.5 1 0.6 0.0 0.0 0.0 0.0 hexenol phenyl ethyl 2 0.0 8 0.0 2.5 2.5 0.0alcohol phenoxy ethyl 0.0 0.0 0.0 0.0 0.5 0.0 0.0 propionate linalool 85 0.0 0.0 0.0 1.5 0.0 cis-3-hexenyl 0.0 0.2 0.0 0.0 0.0 0.0 0.0 acetatelinalyl acetate 0.0 5 0.0 0.0 0.0 1.2 0.0 dihydro myrcenol 0.0 2 to 1000.0 0.0 0.0 0.0 citronellol 0.0 10 0.0 0.0 0.0 1.5 0.0 benzyl acetate0.0 6 0.0 0.0 0.0 4 0.0 verdox 0.0 0.0 7 0.0 0.0 0.0 0.0 triplal 0.0 0.00.6 0.0 0.0 0.2 0.0 alpha terpineol 0.0 0.0 0.0 0.0 0.0 1.2 0.0 dihydroiso 3.5 to 100 0.0 0.2 0.0 2 5 jasmonate cetalox² 0.5 0.2 0.3 2.2 0.00.1 0.0 bacdanol³ 0.1 0.0 1.5 0.0 0.0 0.0 1 undecalactone 1 2 2 0.0 0.010.3 1 lyral³ 10 15 14 0.0 10 2 10 florhydral⁴ 0.0 0.0 0.0 0.0 5 0.0 2cis-3-hexenyl 0.0 2 0.0 0.0 0.0 1.2 2 salicylate indol 0.0 0.0 0.0 0.00.5 0.5 0.0 ethyl vanillin 0.0 0.8 0.7 1.3 0.0 0.0 0.0 heliotropin 0.00.0 0.0 0.0 0.5 0.0 1.6 ebanol⁴ 0.0 2.0 0.0 0.0 0.0 0.0 0.0 gamma 0.00.0 0.0 4.5 0.4 0.0 0.0 decalactone Prunella² 0.0 0.0 0.0 to 100 4 0.00.0 lilial⁴ 0.0 0.0 0.0 0.7 0.0 15 10 benzyl salicylate 0.0 0.0 0.0 0.0to 100 to 100 10 oxocyclohexadecen- 0.0 8 10 1.5 10 0.2 15 2-oneRoselea³ 0.0 0.0 0.0 0.6 0.0 0.0 5 exaltolide 2.5 8 12 0.0 12 0.4 8hexyl cinnamic 2.2 5 0.0 0.0 5 2 0.0 aldehyde zingerone⁴ 0.0 0.5 0.0 0.00.8 0.0 0.0 methyl cedrylone 0.0 3 0.0 0.0 15 0.0 4 eugenol 0.0 0.0 1.30.0 0.0 0.0 0.2 sandela⁴ 0.0 0.0 0.0 0.0 0.0 10 5 methyl dihydro 0.0 0.00.0 0.0 10 10 to 100 jasmonate ionone gamma 0.0 0.0 0.0 0.0 0.0 10 0.0methyl ¹Dragoco Gerberding & Co AG, D-37601 Holzminden GERMANY²Firmenich SA, 1 Route des Jeunes, CH-1211 Geneva 8 SWITZERLAND³International Flavors & Fragrances 521 W. 57th St, New York, NY 10019USA ⁴Givaudan-Roure 19–23 voie des Bans BP98, 95101 Argenteuil Cedex,FRANCE

The perfume raw materials were mixed with stirring at room temperature.

Fragrance Compositions Examples VIII–XII

VIII (% wt) IX (% wt) X (% wt) XI (% wt) XII (% wt) Fragrance 10 12.5 151.5 12 (selected from examples I–VII) Cyclic 2.5 5 10 2.5 0.0Oligosaccharide⁵ Pro-perfume I⁶ 0.0 0.0 0.0 0.0 0.4 Pro-perfume II⁷ 0.00.0 0.0 0.0 0.4 Ethanol to 100 to 100 to 100 to 100 to 100 DeionisedWater 15.75 13 11.5 15.8 0.0 ⁵Beta W7 M available from Wacker-ChemieGmbH, Hanns-Seidel-Platz 4, Munchen, DE ⁶Pro-perfume comprisingoxazolidine pro-melonal, Procter & Gamble, Cincinnati, Ohio ⁷Pro-perfumecomprising beta-amino ketone pro-damascone, Procter & Gamble,Cincinnati, Ohio

The cyclic oligosaccharide was dissolved in ethanol at room temperaturewith stirring. Then the fragrance and water were added with stirring.

Cosmetic Compositions Examples XIII–XV

XIII (% wt) XIV (% wt) XV (% wt) Fragrance (selected from 3 2 3 examplesI–VII) Cyclic Oligosaccharide⁵ 2 1.5 3 Zinc phenolsulphonate 2 1 2Dipropylene Glycol 30.5 17 14.5 Isopropyl myristate 1.5 7 7 Ethanol to100 to 100 to 100 ⁵Beta W7 M available from Wacker-Chemie GmbH,Hanns-Seidel-Platz 4, Munchen, DE

The zinc phenolsulphonate is stirred into the ethanol until fullydissolved. Then the dipropylene glycol is added with stirring. Next theisopropyl myristate, then the cyclic oligosaccharide and then thefragrance are all added with stirring. For an aerosol deodorant apropellant such as propane butane (CAP 40®) can be added to ExamplesXII–XIV according to standard industry practice.

When examples VIII–XV were applied to the substrate the light, fresh,fruity, citrus, green or delicate floral “top note” fragrance characterscould still be determined at least two hours after application. Bycontrast, the same long lasting “top note” effect was not achieved whencontrol compositions, comprising the same fragrance oil but without theentrapment material, were applied to a substrate.

1. A composition comprising: (a) a fragrance oil, wherein the fragranceoil comprises about 5% or greater, by weight of fragrance oil, of one ormore top note perfume raw materials, and wherein the top note perfumeraw materials have a boiling point of less than, or equal to, about 250°C. at 1 atmosphere pressure; (b) an entrapment material which is notpro-associated with the fragrance oil prior to inclusion into thecomposition, the entrapment material being selected from the groupconsisting of polymers; capsules, microcapsules and nanocapsules;liposomes; pro-perfumes selected from more than 1 type of pro-chemistry;film formers absorbents; cyclic oligosaccharides and mixtures thereof;(c) greater than about 50%, by weight, of a volatile solvent; and (d)from about 5% to about 20% water, by weight of the composition.
 2. Acomposition according to claim 1 wherein the top note perfume rawmaterials are selected from aldehydes with a relative molecular mass ofless than or equal to about 200, esters with a relative molecular massof less than or equal to about 225, terpenes with a relative molecularmass of less than or equal to about 200, alcohols with a relativemolecular mass of less than or equal to about 200 ketones with arelative molecular mass of less than or equal to about 200, nitriles,pyrazines, and mixtures thereof.
 3. A composition according to claim 1wherein the top note perfume raw materials of the fragrance oil comprise5% or greater, by weight of the top note perfume raw materials, of topnote perfume raw materials which have an odour detection threshold ofless than, or equal to, 50 parts per billion.
 4. A composition accordingto claim 1 wherein the fragrance oil comprises from about 0.01% to about95%, by weight of fragrance oil, of the middle and base note perfume rawmaterials.
 5. A composition according to claim 1 wherein the middle orbase note perfume raw materials of the fragrance oil comprise 10% orgreater, by weight of the middle and base note perfume raw materials, ofmiddle or base note perfume raw materials which have an odor detectionthreshold of less than, or equal to, 50 parts per billion.
 6. Acomposition according to claim 1 wherein within the fragrance oil theweight ratio of top note perfume raw materials to middle or base noteperfume raw materials is in the range from about 1:20 to about 20:1. 7.A composition according to claim 1 which comprises from about 0.1% toabout 95%, by weight, of said entrapment material.
 8. A compositionaccording to claim 1 wherein the perfume raw material and the entrapmentmaterial exist in an associated form on the substrate and wherein theweight ratio of top note perfume raw material to entrapment materialwithin the associated form is in the range from about 1:20 to about20:1.
 9. A composition according to claim 1 wherein the volatile solventhas a boiling point, at 1 atmosphere pressure, of less than about 150°C.
 10. A composition according to claim 1 wherein the volatile solventis selected from the group consisting of ethers; straight or branchedchain alcohols and diols; volatile silicones; propellants, and mixturesthereof.
 11. A composition according to claim 1 an wherein thecomposition is a cosmetic composition.
 12. A composition comprising: (a)a fragrance oil, wherein the fragrance oil comprises about 5% orgreater, by weight of fragrance oil, of one or more top note perfume rawmaterials, and wherein the top note perfume raw materials have a boilingpoint of less than, or equal to, about 250° C. at 1 atmosphere pressure;(b) an entrapment material which is not pre-associated with thefragrance oil prior to inclusion into the composition, the entrapmentmaterial being selected from the group consisting of α-cyclodextrin,β-cyclodextrin, methyl-α-cyclodextrin, methyl-β-cyclodextrin, andmixtures thereof; (c) greater than about 50% of a volatile solvent; and(d) from about 5% to about 20% water, by weight of the composition. 13.A method for fragrancing a substrate, the method comprising the step ofapplying a composition to the substrate, the composition comprising: (a)a fragrance oil comprising about 5% or greater, by weight of fragranceoil, of one or more top note perfume raw materials, and wherein the topnote perfume raw materials have a boiling point of less than, or equalto, about 250° C. at 1 atmosphere pressure; (b) an entrapment materialwhich is not pre-associated with the fragrance oil prior to inclusioninto the composition, the entrapment material selected from the groupconsisting of polymers; capsules, microcapsules and nanocapsules;liposomes; pro-perfumes selected from more than 1 type of pro-chemistry;film formers; absorbents; cyclic oligosaccharides and mixtures thereof;and (c) greater than about 50%, by weight, of a volatile solvent;whereupon after application to the substrate, at least some of thefragrance oil and the entrapment material form a reversible physical orchemical association.
 14. The method of claim 13, wherein the entrapmentmaterial comprises cyclic oligosaccharides selected from the groupconsisting of α-cyclodextrin, β-cyclodextrin, methyl-α-cyclodextrin,methyl-β-cyclodextrin, and mixtures thereof.